Bio-based adhesive compositions for coating applications

Abstract

An aqueous polymer dispersion of a copolymer comprising monomers a), b), c) and d). Monomer a) has the structure (I): (I) wherein R1 is hydrogen or methyl; and R2 is a C1-C8 non-cyclic alkyl group. Monomer b) is an ethylenically unsaturated monomer different from a) selected from the group consisting of C1-C8 alkyl (meth) acrylates, ethylene, vinyl acetate, vinyl versatate, styrene, styrene derivatives, or combinations thereof. Monomer c) is an ethylenically unsaturated monomer comprising a functional group selected from the group consisting of carboxylate, phosphate, phosphonate; sulfonate and / or acid, and / or salt, and / or anhydride forms thereof; a hydroxyl group; a silane; or a combination thereof. Monomer d) is a nitrogen-containing ethylenically unsaturated monomer. The copolymer comprises a biochar content of at least 5% as determined according to ASTM D6866-22. The minimum film-forming temperature of the aqueous dispersion is less than 30 DEG C.

Description

Technical Field

[0001] Bio-based acrylate polymers suitable for use as coating adhesives. Background Technology

[0002] Coatings are widely used in building, industrial, and construction applications. Acrylic emulsion polymers are used as adhesives in these applications due to their good balance of performance and cost. Desired coating properties affected by adhesives include scrub resistance, tinting strength, anti-blocking properties, and stain resistance. Acrylic emulsion polymers are derived from petroleum-based propylene. With dwindling oil supplies and the intensifying effects of climate change, there is a desire to find new methods to synthesize acrylic emulsion polymers with lower product carbon footprints.

[0003] One approach to reducing petroleum-derived contents in acrylic emulsion polymers is to incorporate bio-based materials through blending. However, many polymer pairs are chemically incompatible. This incompatibility typically leads to performance degradation rather than synergistic performance benefits.

[0004] To increase the biocarbon content (BCC) of aqueous polymer dispersions containing acrylic polymers while maintaining or improving the performance of the resulting coating compositions, another approach is to polymerize acrylic monomers containing a certain amount of biorenewable material via emulsion polymerization. However, the challenge lies in producing acrylic copolymers from available bio-based acrylic monomers while achieving the performance required for the intended application and sustainability goals, specifically a minimum BCC threshold of 22% for acrylic copolymers according to ASTM-6866-22 Method B.

[0005] US 10662273 relates to an aqueous copolymer dispersion formed by emulsion polymerization of a monomer mixture, the monomer mixture comprising one or more (meth)acrylates having a glass transition temperature (Tg) above 25°C for the homopolymer, and at least one (meth)acrylate having a biorenewable carbon content of at least 50% by weight of the total carbon content of the ester.

[0006] US 9593191 relates to the use of polymers obtained by polymerizing 2-octyl acrylate from renewable sources and optionally at least one other monomer as a binder for coating compositions or for the production of coating compositions.

[0007] US 9505943 relates to a waterborne polymer coating composition comprising at least: a vinyl polymer A having a weight-average molecular weight of 1,000 to 150,000 and an acid value of at least 5 mg KOH / g; and a vinyl polymer B having a molecular weight Mw of at least 80,000 g / mol and an acid value of less than 35 mg KOH / g; wherein at least 20% by weight of polymer A and / or polymer B is derived from at least one biorenewable olefinic unsaturated monomer.

[0008] US 9458346 relates to an aqueous polymer dispersion containing at least two phases of vinyl polymers, said two phases comprising: A) 40-90 wt% of vinyl polymer A with a glass transition temperature in the range of -50 to 30°C; and B) 10-60 wt% of vinyl polymer B with a glass transition temperature in the range of 50 to 130°C; and at least 20 wt% of the monomer composition for forming vinyl polymer A and vinyl polymer B is derived from at least one biorenewable olefinic unsaturated monomer.

[0009] US 8642696 relates to copolymer compositions and methods for preparing such compositions. The copolymers comprise a vinyl aromatic monomer; a second monomer; and a bio-based monomer comprising isobornyl methacrylate and tetrahydrofurfuryl methacrylate.

[0010] US 2021 / 0324114 relates to an aqueous dispersion as a bio-based adhesive and an aqueous coating composition comprising the aqueous dispersion, exhibiting stain resistance, freeze-thaw stability and anti-clogging properties.

[0011] CN 112300343 A relates to a bio-based acrylic emulsion for use in interior wall coatings and a method for preparing the same. According to test results from ASTM D6866, the bio-based acrylic emulsion disclosed in this invention exhibits excellent physicochemical properties and a bio-based content exceeding 25%.

[0012] EP 2626397 relates to polyacrylate-based pressure-sensitive adhesives.

[0013] WO2022 / 033945 relates to aqueous vinyl polymer dispersions comprising hydrophilic vinyl oligomers, hydrophobic vinyl oligomers, and vinyl polymers obtained by emulsion polymerization of olefinic unsaturated monomers from petrochemical or renewable sources.

[0014] WO2023 / 148332 relates to an aqueous polymer latex that can be obtained by free radical emulsion polymerization of monomer composition M in the optional presence of seed latex. Summary of the Invention

[0015] Aqueous polymer dispersions containing bio-based monomers provide coating compositions with high bio-carbon content, and when used as a binder in aqueous polymer dispersions in coating compositions, they surprisingly offer a balance of scrub resistance, tinting strength, anti-blocking properties, and stain resistance.

[0016] An aqueous polymer dispersion is provided. The aqueous polymer dispersion comprises at least one copolymer formed by emulsion polymerization of a monomer mixture comprising the following monomers a), b), c), and d), expressed in weight percent based on the total dry weight of the copolymer.

[0017] a) 20-80% by weight of at least one monomer of structure I: (I)

[0018] Where R 1 It is hydrogen or methyl; R 2 It is a non-cyclic alkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is below 25°C. Monomer a) is preferably bio-based.

[0019] b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: C1-C8 alkyl esters of (meth)acrylate, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives, or combinations thereof. Monomer b) is optionally bio-based.

[0020] c) 0.1-10% by weight of at least one olefinic unsaturated monomer comprising at least one functional group comprising at least one of the following: carboxyl, phosphate, phosphonate; sulfonate, and / or an acid, and / or salt, and / or anhydride form of any of the foregoing; hydroxyl; silane; or combinations thereof.

[0021] d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer.

[0022] The copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content (as determined according to ASTM D6866-22 Method B). The minimum film-forming temperature of the aqueous polymer dispersion is 30°C or lower.

[0023] A coating composition is also provided. The coating composition comprises an aqueous polymer dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture. Based on the total dry weight of the copolymer, the monomer mixture comprises monomers a), b), c), and d) as shown below.

[0024] a) 20-80% by weight of at least one monomer of structure I: Where R 1 It is hydrogen or methyl; R 2 It is a non-cyclic alkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is below 25°C. Monomer a) is preferably bio-based.

[0025] b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: C1-C8 alkyl esters of (meth)acrylate, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives, or combinations thereof. The monomer may optionally be bio-based.

[0026] c) 0.1-10% by weight of at least one olefinic unsaturated monomer comprising at least one functional group comprising at least one of the following: carboxyl, phosphate, phosphonate; sulfonate, and / or an acid, and / or salt, and / or anhydride form of any of the foregoing; hydroxyl; silane; or combinations thereof.

[0027] d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer.

[0028] The copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content (as determined according to ASTM D6866-22 Method B). The minimum film-forming temperature of the aqueous dispersion is 30°C or lower. Compared to coating compositions not containing the aqueous dispersion of this disclosure, the dried layer of the coating composition is improved in one or more, preferably two or more, and most preferably all four, of the following criteria: scrub resistance as measured according to ASTM D2486-17 Method B and / or as described in the examples; tinting strength as measured according to ASTM D4838-88 (2016) and / or as described in the examples; anti-blocking property as measured according to ASTM D4946-89 (2017) and / or as described in the examples; and / or stain resistance expressed as ΔE as measured according to ASTM D4828-94 (2020) and / or as described in the examples.

[0029] Brief description of the attached figures

[0030] Figure 1 The photographs show the removal of lipstick stains from a comparative coating composition and a coating composition according to an embodiment of the present invention. Detailed Implementation

[0031] As used herein, the term "bio-based" refers to products or materials that are wholly or partially derived from biomass resources (i.e., derived from biomass). Biomass resources are renewable or periodically available organic materials, such as crop residues, wood residues, grasses, and aquatic plants. Products or materials, monomers, or polymers containing any amount of bio-based content are referred to as "bio-based."

[0032] As used herein, the term "non-bio-based" refers to a product that does not contain any bio-based materials. For example, a product made entirely from petrochemical resources is called a non-bio-based product.

[0033] Biobased / bio-based content (BCC) is the ratio of carbon derived from biomass in a product to its total organic carbon (TOC). BCC is determined according to ASTM D6866-22 Method B. According to ASTM D6866-22 Method B, the biocarbon content of a product is reported as a fraction of total organic carbon, not based on its weight.

[0034] Unless otherwise stated, all percentages in this article are weight percentages.

[0035] As used herein, “polymer” is intended to include organic molecules with a weight-average molecular weight greater than 20,000 g / mol, preferably greater than 50,000 g / mol, as measured by gel permeation chromatography.

[0036] BCC content of copolymer

[0037] The copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content (as determined according to ASTM D6866-22 Method B). According to some embodiments, the copolymer contains at least 22, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or up to 100% BCC (as determined according to ASTM D6866-22).

[0038] Properties of copolymers

[0039] The minimum film-forming temperature of the aqueous dispersion of the copolymer, as measured according to ASTM D2354-10 (2018), can be below 30°C. According to some embodiments, the minimum film-forming temperature of the aqueous dispersion of the copolymer can be below 25, 20, 15, 10, 5, or below 0°C.

[0040] According to some embodiments, the Tg of the copolymer calculated by the Fox equation can be below 25, 20, 15, 10, 5, or 0 °C. As is known in the art, the Tg calculated by the Fox equation uses known values ​​for the homopolymers of the copolymer copolymers. These homopolymer Tg values ​​are those reported in Polymer Handbook, 4th Edition; J. Brandrup (ed.), EH Immergut (ed.), EAGrulke (ed.); ISBN: 978-0-471-47936-9, mid-May 2003.

[0041] According to some embodiments, the copolymer can be a single-stage polymer excluding the seed polymer. According to other embodiments, the copolymer can be a two-stage polymer, each stage having a different composition excluding the seed polymer. According to still other embodiments, the copolymer can be a multi-stage polymer, i.e., comprising three or more stages, each stage having a different composition excluding the seed polymer.

[0042] According to one embodiment, the total percentage of monomers a), b), c), d) and optional additional monomers in the copolymer is 100%.

[0043] Monomers in copolymers

[0044] Monomer a)

[0045] The copolymer contains 20-80% by weight of one or more monomers of structure (I): (I) Where R 1 It is hydrogen or methyl; R 2 It is a non-cyclic alkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is below 25°C. According to some embodiments, Tg is preferably below 20°C, more preferably below 10°C.

[0046] Monomer a) is preferably bio-based. The biocarbon content of monomer a) may be at least 5%, preferably at least 10%, more preferably at least 20%, and most preferably at least 30% (as determined according to ASTM D6866-22 Method B). According to some embodiments, monomer a) contains at least 5%, preferably at least 10%, more preferably at least 20%, most preferably at least 30%, very preferably at least 40%, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99%, or up to 100% biocarbon content (BCC) (as determined according to ASTM D6866-22).

[0047] According to some embodiments, based on the total dry weight of the copolymer, the copolymer comprises at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or at least 75% by weight of monomer a) or a mixture of monomer a). According to some embodiments, based on the total dry weight of the copolymer, the copolymer comprises at most 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or at most 25% by weight of monomer a).

[0048] According to one embodiment, the copolymer comprises 45-60% by weight of monomer a), and monomer a) comprises at least one of the following: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-methylbutyl methacrylate, various isomers of pentyl methacrylate, various isomers of hexyl methacrylate, various isomers of heptyl methacrylate, various isomers of octyl methacrylate, 2-octyl methacrylate, or combinations thereof.

[0049] According to one embodiment, monomer a) comprises at least one of the following: ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate (e.g., n-butyl methacrylate), isobutyl methacrylate, tert-butyl methacrylate; 2-methylbutyl methacrylate, heptyl methacrylate, octyl methacrylate (e.g., 2-octyl methacrylate); or combinations thereof.

[0050] Other non-limiting examples of monomer a) are acyclic C1-C8 acrylates, acyclic C1-C8 methacrylates, or mixtures thereof, wherein the homopolymer or copolymer has the above-mentioned Tg range. For example, monomer a) may be at least one of the following: ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methylbutyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, ethyl butyl (meth)acrylate, various isomers of pentyl (meth)acrylate, various isomers of hexyl (meth)acrylate, various isomers of heptyl (meth)acrylate (e.g., n-heptyl (meth)acrylate), various isomers of octyl (meth)acrylate, or combinations thereof. More preferably, C1-C6 (meth)acrylates, most preferably C1-C4 (meth)acrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and isobutyl acrylate.

[0051] Monomer b)

[0052] The copolymer also contains 20-80% by weight of at least one olefinically unsaturated monomer or mixture of monomers, which is different from monomer a). Monomer b) may be selected from the group consisting of: C1-C8 alkyl esters of (meth)acrylate, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives, or combinations thereof, based on the total dry weight of the copolymer. Monomer b) is optionally bio-based. If monomer b) is bio-based, it may contain at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or up to 100% BCC (as determined according to ASTM D6866-22 Method B).

[0053] According to one embodiment, monomer b) comprises methyl (meth)acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

[0054] According to some embodiments, based on the total dry weight of the copolymer, the copolymer contains at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or at least 75% by weight of monomer b). According to some embodiments, based on the total dry weight of the copolymer, the copolymer contains at most 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or at most 25% by weight of monomer b).

[0055] According to one embodiment, the copolymer may contain 40-55% by weight of monomer b), and monomer b) comprises at least one of the following: methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, styrene, or a combination thereof.

[0056] Monomer c)

[0057] Based on the total dry weight of the copolymer, the copolymer comprises 0.1-10% by weight of at least one olefinically unsaturated monomer or mixture of monomers, said monomer comprising at least one functional group comprising at least one of the following: carboxyl groups and / or their acid, and / or salt, and / or anhydride forms; phosphate groups and / or their acid, and / or salt forms; phosphonates and / or their acid, and / or salt forms; sulfur-containing monomers and / or their acid, and / or salt forms; sulfonates and / or their acid, and / or salt forms; hydroxyl groups; silanes; or combinations thereof.

[0058] According to one embodiment, monomer c) comprises at least one of the following: a carboxylic acid functionalized monomer, a phosphate-containing monomer, a sulfur-containing monomer, or a combination thereof.

[0059] Non-limiting examples of monomer c) are acrylic acid, methacrylic acid, or combinations thereof.

[0060] Other non-limiting examples include carboxylic acid functionalized comonomers, such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, or combinations thereof.

[0061] Acid-functionalized comonomers selected from phosphoric or sulfur-based acid-functionalized monomers or phosphate ester comonomers may be used, non-limiting examples of which include, for example: alkyl (meth)acrylates of phosphate; alkyl (meth)acrylamide of phosphate; alkyl crotonate of phosphate, alkyl maleate of phosphate, alkyl fumarate of phosphate, dialkyl (meth)acrylate of phosphate, dialkyl crotonate of phosphate, vinyl phosphate or (meth)allyl phosphate; phosphate esters of polypropylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate; polyoxyethylene allyl ether phosphate, or vinylphosphonic acid.

[0062] Sulfoyl comonomers include, but are not limited to, vinyl and allyl sulfonic acids; ethyl (meth)acrylate sulfonate, aryl sulfonic acids; (meth)acrylamidoethane sulfonic acid; methacrylamido-2-methylpropane sulfonic acid; and alkali metal salts of sulfonic acids.

[0063] Other functional monomers (c) are monomers containing at least one hydroxyl and / or silane group. Preferred examples are 2-hydroxy-3-phenoxypropyl methacrylate, (meth)acryloyloxyalkyltrialkoxysilane, vinyltrialkoxysilane, hydroxyalkyl (meth)acrylate, or combinations thereof; preferably, 4-hydroxybutyl acrylate, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or combinations thereof; more preferably, vinyltrialkoxysilane, [3-(methacryloyloxy)propyl]trimethoxysilane, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, or combinations thereof.

[0064] According to some embodiments, based on the total dry weight of the copolymer, the copolymer comprises at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9 or at least 9.5% by weight of monomer c). According to some embodiments, based on the total dry weight of the copolymer, the copolymer may comprise up to 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5 or up to 1% by weight of monomer c).

[0065] According to one embodiment, the copolymer may contain 0.1-2% by weight of monomer c), and monomer c) may contain at least one carboxylate functional group and / or its acid, and / or salt, and / or anhydride form.

[0066] Monomer d)

[0067] The copolymer contains 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer (d) or a mixture of monomers (d).

[0068] According to one embodiment, the copolymer comprises at least one of the following: (meth)acrylamide, diacetone acrylamide, (meth)acrylate urea, or a combination thereof.

[0069] Other non-limiting examples of monomer d) are urea (meth)acrylates, meth)acrylates having at least one of urea and thiourea in the side chain; acrylic allophanes, aminoalkyl (meth)acrylates, dialkylamino (meth)acrylates, aminoethyl acrylates and aminoethyl methacrylates; dimethylaminoethyl acrylates and dimethylaminoethyl methacrylates; diethylaminoethyl acrylates and diethylaminoethyl methacrylates, dimethylaminopropyl acrylates and dimethylaminopropyl methacrylates; 3-dimethylamino-2,2-dimethylpropyl acrylates and 3-dimethylamino-2,2-dimethylpropyl methacrylates; aminoethyl methacrylates, N-(2-aminoethyl)(meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide, 2-(diethylamino)ethyl(meth)acrylates, 2-(diisopropylamino)methacrylates Ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, N-[2-(diethylamino)ethyl](meth)acrylamide, 2-morpholinoethyl (meth)acrylate, N-morpholinoethyl acrylate and N-morpholinoethyl methacrylate; 2-N-piperidinyl ethyl acrylate and 2-N-piperidinyl ethyl methacrylate; N-(3-dimethylaminopropyl)acrylamide and methacrylamide; N-dimethylaminoethylacrylamide and methacrylamide; N-diethylaminoethylacrylamide and methacrylamide; N-(4-morpholinomethyl)acrylamide and methacrylamide;Vinyl imidazole and monoene unsaturated derivatives of ethylidene urea, such as N-(2-(meth)acryloyloxyethyl)ethylidene, N-(β-acrylamidoethyl)ethylidene, N-2-(allyl carbamate)aminoethylimidazolium ketone, N-vinyl ethylidene urea, N-(3-allyloxy-2-hydroxypropyl)aminoethyl ethylidene urea, N-ethyleneoxyethylidene urea, N-methacryloyloxyacetoxyethyl ethylidene urea, N-(acrylamidoethylidene)ethylidene urea, N-(methacrylamidoethylidene)ethylidene urea, 1-(2-methacryloyloxyethyl)-2-imidazolium ketone, N-(methacrylamidoethyl)... Ethylene urea, N-(2-methacryloyloxyethyl)ethylene urea, N-(2-methacryloyloxyacetamidoethyl)-N,N'-ethylene urea, allylalkyl ethylene urea, N-methacrylamidomethyl urea, N-methacryloyl urea, N-[3-(1,3-diazacyclohexane)-2-one-propyl]methacrylamide, 2-(1-imidazolyl)ethyl methacrylate, 2-(1-imidazolyl-2-one)ethyl methacrylate, N-(methacrylamido)ethyl urea, carbamate methacrylate, acrylamide, methacrylamide, acrylonitrile, vinyl cyanide, vinylpyrrolidone, or combinations thereof. According to one embodiment, monomer d) comprises a monomer containing one or more carbonyl groups. If present, these carbonyl groups can react with a crosslinking additive containing one or more hydrazine or acylhydrazine groups to form a crosslink. Non-limiting examples of suitable monomers of this kind are those containing carbonyl groups or 1,3-dicarbonyl groups. Diacetone acrylamide is preferred.

[0070] According to some embodiments, based on the total dry weight of the copolymer, the copolymer contains at least 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9 or at least 9.5% by weight of monomer (d). According to some embodiments, based on the total dry weight of the copolymer, the copolymer may contain up to 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5 or up to 1% by weight of monomer (d).

[0071] According to one embodiment, the copolymer may contain 1-5% by weight of monomer d), and monomer d) contains at least one of (meth)acrylamide, diacetone acrylamide, or a combination thereof.

[0072] According to one embodiment, the copolymer does not contain acetyl acetoxyethyl methacrylate (AAEM).

[0073] According to one embodiment, the copolymer contains less than 0.1, 0.05, or 0.01% by weight of itaconic acid ester, based on the total weight of the copolymer. According to one embodiment, the copolymer does not contain itaconic acid ester.

[0074] According to one embodiment, the copolymer contains less than 0.1, 0.05, or 0.01% by weight of itacamide, based on the total weight of the copolymer. According to one embodiment, the copolymer does not contain itacamide.

[0075] According to one embodiment, based on the total weight of the copolymer, the copolymer comprises less than 0.1, 0.05, or 0.01% by weight of cyclic monomers, such as isobornyl methacrylate or tetrahydrofurfuryl methacrylate, alone or in combination. According to one embodiment, the copolymer does not contain cyclic monomers, such as isobornyl methacrylate or tetrahydrofurfuryl methacrylate, alone or in combination.

[0076] Additional free radical reactive compounds: The copolymer may optionally contain 0-2% by weight of at least one free radical other than monomer a), monomer b), monomer c), or monomer d). reactive compounds Additional free radicals reactive compounds The copolymer may be optionally wholly or partially bio-based, or may not be bio-based. The copolymer may contain the following additional free radicals. reactive compounds One, some, or all of them. If more than one additional [item] is present during emulsion polymerization. reactive compounds Based on the total weight of the copolymer, the copolymer may contain 0-2% by weight of each additional free radical. reactive compounds or all additional free radicals reactive compounds Total 1-2% by weight. According to some embodiments, based on the total weight of the copolymer, the copolymer may contain at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.3, 1.4, or at least 1.5% by weight of each additional free radical. Reactive compounds thing or all additional free radicals reactive compounds The total amount is at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.3, 1.4, or at least 1.5% by weight. According to some embodiments, based on the total weight of the copolymer, the copolymer may contain up to 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, or up to 1% by weight of each additional free radical. Reactivity Compounds or all additional free radicals reactive compounds Total weight up to 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1 or up to 1.

[0077] Additional free radicals reactive compounds Non-limiting examples include chain transfer agents, particularly sulfur-containing chain transfer agents, such as 3-mercaptopropionic acid, n-dodecyl mercaptan, tert-dodecyl mercaptan, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, isooctyl 3-mercaptopropionate, thiophenol, alkyl azelaic acid mercaptan, or mixtures thereof. Other non-limiting examples of chain transfer agents are thiols, polythiols, polyhalogenated compounds, and allyl compounds in the polymerization mixture. Such chain transfer agents can be used to adjust the molecular weight of the polymer. Suitable examples of chain transfer agents include 3-mercaptopropionic acid, n-dodecyl mercaptan, tert-dodecyl mercaptan, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, isooctyl 3-mercaptopropionate, thiophenol, alkyl azelaic acid mercaptan, or mixtures thereof. Chain transfer agents can be used in effective amounts to control the molecular weight of the emulsion polymer, for example, based on 0 to 1 wt%, 0.1 wt% to 0.5 wt%, or 0.15 wt% to 0.4 wt% of the total weight of the monomers used to prepare the emulsion polymer.

[0078] It also applies to additional free radicals. reactive compounds Monomers containing two or more unsaturated carbon-carbon double bonds, capable of free radical polymerization, including but not limited to tripropylene glycol diacrylate, 1,3-butanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, 1,3 -Butanediol dimethacrylate, 1,4-Butanediol dimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, 1,10-decanediol diacrylate, ethoxylated (2) bisphenol A diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diallyl phthalate, allyl methacrylate, divinylbenzene or combinations thereof.

[0079] Copolymerizable surfactants may also be included in the final polymer as additional radical reactive compounds. Non-limiting examples of copolymerizable stabilizers used in this aqueous dispersion are copolymerizable nonionic and anionic surfactants, such as those disclosed in US2014 / 0243552, the entire disclosure of which is incorporated herein by reference for all purposes. Other suitable copolymerizable surfactants are marketed under the trade name Hitenol. ® BC, Hitenol ® KH, Hitenol ®AR, AdekaReasoap SR and AdekaReasoap ER, Oximulsion ® React sales.

[0080] Any one or all of these additional monomers or radical reactive compounds may be present in the copolymer at 0-2% by weight based on the total dry weight of the copolymer.

[0081] Aggregation methods : Emulsion polymers and monomers used to prepare polymer emulsions or dispersions are known in the art (as discussed in texts on the subject, such as DC Blackley’s “Emulsion Polymerization: Theory and Practice” published by Wiley in 1975, F.A. Bovey et al.’s “Emulsion Polymerization” published by Interscience in 1965, and PA Lovell et al.’s “Emulsion Polymerization and Emulsion Polymers” published by Wiley Science in 1997).

[0082] The aqueous dispersion of the present invention comprises one or more emulsion polymers prepared by emulsion polymerization, which are well known in the art.

[0083] Emulsion polymers can be prepared by emulsion polymerization of a monomer mixture comprising the monomers a), b), c), and d) described above, as well as optional additional monomers. The monomer mixture can be added directly or as an aqueous emulsion; or it can be added once or multiple times, or continuously, linearly, or non-linearly, during the reaction to prepare the emulsion polymer. Monomer emulsions containing all or part of the monomers to be polymerized can be prepared using monomers, water, and surfactants.

[0084] Emulsion polymers can be prepared as single-stage or multi-stage polymers.

[0085] One or more surfactants may be added before, during, or after the polymerization of the monomer mixture or its combination. These surfactants may include anionic and / or nonionic emulsifiers. Examples of suitable nonionic emulsifiers include acyl, alkyl, oleyl, alkylaryl ethoxylates, and copolymers of ethylene oxide and propylene oxide. These products are commercially available, for example under the name Genapol. ® Lutensol ® or Emulan ®Rhodasurf ® Tergitol™ and Pluronic™. These include, for example, C4 to C12 monoalkylphenol ethoxylates, dialkylphenol ethoxylates and trialkylphenol ethoxylates (EO range 3 to 70), C8 to C18 fatty alcohol ethoxylates, C11-C15 oxo-process alcohol ethoxylates, C16 to C18 fatty alcohol ethoxylates, C11 oxo-process alcohol ethoxylates, and C13 oxo-process alcohol ethoxylates. Some commercially available anionic surfactants include sodium, potassium, and ammonium salts of linear and branched alcohol sulfates (e.g., Stepan's Polystep). ® B-5, B-7), alcohol ether sulfates (e.g., BASF's Disponil) ® FES 32, FES77 and FES993, and Stepan's Polystep ® B-11, B-12, B-19, B-20, B-22, B-23, B-40, B-41, etc.), linear and branched alkylbenzene sulfonates (e.g., Stepan's Polystep). ® A-15 and A-16), α-olefin sulfonates (e.g., Stepan's Polystep). ® A-18 and Solvay's Rhodacal ® DS-4), linear and branched alkyl diphenyl ether disulfonates (e.g., Dowfax 2A-1 from The Dow Chemical Company and Calfax from Pilot Chemical). ® DB-45 and Calfax ® 16L-35); sulfosuccinates (e.g., Solvay's Aerosol) ® A-102, OTPG-75, MA-80I, etc.), phosphate esters (e.g., Solvay's Rhodafac) ® RS-610 and Stepan's Polystep ® P-11, P-12, P-13), stilbene phenol sulfate, tristilbene phenol sulfate, stilbene phenol phosphate, and tristilbene phenol phosphate (e.g., Stepan's Polystep). ®The amount of surfactant used can typically be from 0 to 5 wt%, 0.1 wt% to 3 wt%, or 0.2 wt% to 2 wt% based on the total weight of the monomers.

[0086] As mentioned above, stabilizers also applicable to this dispersion are copolymerizable nonionic and anionic surfactants, such as those disclosed in US2014 / 0243552. Other suitable copolymerizable surfactants are marketed under the trade name Hitenol. ® BC, Hitenol ® KH, Hitenol ® AR, Adeka Reasoap SR and Adeka Reasoap ER, Oximulsion ® React sales.

[0087] The polymerization process can be thermally initiated or redox-initiated emulsion polymerization. Examples of suitable free radical initiators include hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium and / or alkali metal persulfates, sodium perborate, superphosphate and their salts; potassium permanganate. Free radical initiators can generally be used at a content of 0.01% to 3.0% by weight based on the total weight of the monomers. Redox systems comprising the above initiators coupled with suitable reducing agents can be used in the polymerization process. Examples of suitable reducing agents include sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, alkali metal salts and ammonium salts of sulfur-containing acids (e.g., sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium dithionite), sulfides, hydrosulfides or dithionites, formadinesulfinic acid, acetone bisulfite, glycolic acid, hydroxymethanesulfonic acid, glyoxylate hydrate, lactic acid, glyceric acid, malic acid, tartaric acid and salts of the aforementioned acids. Metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, or cobalt can be used to catalyze redox reactions. Metal chelating agents may be used optionally.

[0088] The suitable temperature for the polymerization process can be below 100°C, in the range of 30 to 95°C, or in the range of 50 to 90°C. The emulsion polymerization can be seeded or seedless. In another aspect of the invention, the aqueous acrylic emulsion polymer can be prepared by a multi-stage emulsion polymerization process, wherein at least two compositionally different stages are polymerized sequentially, as described above.

[0089] Additives in aqueous dispersions: Aqueous dispersions may also contain water-soluble or water-dispersible crosslinking agents. These crosslinking agents may be referred to as potential crosslinking agents. Such crosslinking agents will react with specific polymer functional groups (e.g., carbonyl or 1,3-dicarbonyl) when water is removed from the coating composition described herein and a film or coating is formed from the coating composition. Types of water-soluble crosslinking agents that can be used in the compositions described herein include compounds containing at least two hydrazine and / or acylhydrazine moieties. Particularly suitable are dihydrazine compounds of aliphatic dicarboxylic acids, such as oxalate dihydrazine, malonate dihydrazine, succinate dihydrazine, glutarate dihydrazine, adipic acid dihydrazine, maleate dihydrazine, fumarate dihydrazine, and / or itaconic acid dihydrazine. Adipic acid dihydrazine (ADH) is a preferred water-soluble crosslinking agent for use in the compositions described herein, especially those produced from monomer compositions containing diacetone acrylamide (DAAM). As mentioned above, DAAM may be included as at least one nitrogen-containing olefinic unsaturated monomer (d) or a mixture of monomers (d). DAAM contains a carbonyl group that reacts with a potential crosslinking agent.

[0090] In one embodiment, the aqueous dispersion described herein further comprises one or more additives to improve the surface properties of a dried coating comprising the aqueous dispersion. Non-limiting examples of such additives include waxes, fluorinated surfactants, silicone surfactants, rhamnolipid-based surfactants, and phosphate ester surfactants. These performance additives are commercially available, for example under names such as Capstone™ and Aquacer. ® Dowsil™, Stepcote ® Commonly used fluorinated surfactants include, for example, fluoroalkanes, perfluoroalkanes, and their derivatives. In one aspect, short-chain fluorinated compounds are preferred. In a preferred aspect, the fluorinated surfactant is anionic C6 fluorocarbons (e.g., Capstone). ® FS-61), and preferably substantially free of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Wax additives can be derived from both fossil and renewable sources and are typically included in aqueous dispersions and coatings to improve water resistance, surface smoothness, and anti-blocking properties. Non-limiting examples include paraffin-based wax emulsions (e.g., BYK's Aquacer 497 and Aquacer 539, Michelman's Michem). ® Emulsion 36840, BASF's Joncryl ® Wax 35). Examples of silicone surfactants may include Dow's DOWSIL™ 211S Additive. Examples of phosphate ester surfactants include Stepan's Stepcote. ®W-877, W-839, and W-843. Non-limiting examples are potassium, sodium, or lithium n-octyl phosphate, more preferably potassium n-octyl phosphate, and most preferably potassium salts of n-octyl phosphate (e.g., Stepcote). ® (W-877). Based on the total weight of the coating composition, the additives used are typically 50 ppm to 5000 ppm, 100 to 4000 ppm, preferably 200 to 3000 ppm, and most preferably 250 to 2500 ppm. These additives may be added before, during, or after polymerization.

[0091] The aqueous dispersion may also contain one or more surfactants discussed in the polymerization section.

[0092] According to some embodiments, it is desirable that the aqueous dispersion obtained by the present invention contains low levels of coagulants, for example, below 1,000 ppm, below 800 ppm, below 500 ppm, below 400 ppm, below 300 ppm, or even below 200 ppm. Coagulants are defined as filterable material, meaning the undesirable coarse material formed by coagulated latex particles during the polymerization process.

[0093] Coating composition

[0094] A coating composition is also provided. The coating composition comprises an aqueous polymer dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture, the monomer mixture comprising monomers a), b), c), and d) based on the total dry weight of the copolymer.

[0095] BCC content of coating composition

[0096] The BCC of the coating composition is determined according to ASTM-6866-22 Method B. According to some embodiments, the coating composition contains at least 5, 10, 15, 20, 22, 25, 30, 35, 40, 45, 50, 60, 65, 70, 75 or at least 80% BCC (determined according to ASTM-6866-22 Method B).

[0097] According to one embodiment, the BCC of the coating composition is based on all organic carbon in the coating composition, namely, carbon from the binder and carbon from any other additives in the coating composition.

[0098] According to another embodiment, the BCC of the coating composition is based solely on the carbon from the binder in the coating composition.

[0099] Properties of coating compositions

[0100] Compared to coating formulations that do not contain the aqueous polymer dispersions described herein, the dried layer of this coating composition is improved in one, two, three, or all four of the following key performance measurements: for example, scrub resistance as measured according to ASTM D2486-17 Method B and / or as described in the examples; tinting strength as measured according to ASTM D4838-88 (2016) and / or as described in the examples; anti-blocking properties as measured according to ASTM D4946-89 (2017) and / or as described in the examples; and / or stain resistance as measured according to ASTM D4828-94 (2020) and / or as described in the examples.

[0101] Other components in the coating composition

[0102] In addition to the copolymer dispersion, the waterborne coating composition may also contain other components (additives). According to embodiments, some or all of these additional components may be wholly or partially bio-based.

[0103] Such additives include, but are not limited to: crosslinking agents, pH adjusters, UV stabilizers, foam control agents, wetting agents, fillers, pigments, pigment extenders, dyes, matting agents and texturing agents, pigment enhancers, emulsifiers, surfactants, dispersants, curing agents, coalescing agents, wetting agents, biocides, thickeners, rheology modifiers, plasticizers, waxes, antioxidants, defoamers, antisettling agents, antiskinning agents, corrosion inhibitors, dehydrating agents, antigassing agents, dispersing aids, desiccants, antistatic additives, flashcorrosion inhibitors, flotation additives and flooding additives, in-can and in-film preservatives, insecticides, optical brighteners, deodorizers, water-soluble resins, and other reagents used in the art. These include dyes, emulsifiers, rheology control additives, adjunct polymers, pigments or colorants, fillers, dispersants or surfactants, plasticizers, defoamers, thickeners, biocides, solvents, rheology modifiers, wetting agents or spreading agents, leveling agents, conductive additives, insulating fillers, adhesion promoters, anti-blocking agents, anti-cratering agents or anti-crawling agents, corrosion inhibitors, antistatic agents, flame retardants, optical brighteners, UV absorbers or other light stabilizers, antioxidants, chelating agents, leveling agents, humectants, insecticides, lubricants, odorants, oils, waxes or antislip agents, soil repellents, freeze-thaw and / or open time additives, and antifouling agents.

[0104] Non-limiting examples of pigments that can be used as colorants, fillers, or dyes include, but are not limited to: carbon black, colored organic pigments, and metal oxide pigments, such as titanium dioxide, zinc oxide, clay, aluminum silicate, zinc hydroxide, magnesium silicate, calcium silicate, amorphous silica, fumed silica, calcined silica, colloidal silica, aluminum oxide, aluminum hydroxide, zirconium oxide, and cerium oxide, as well as calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, and zinc carbonate.

[0105] Pigments include colored pigments and opaque pigments. Pigment volume concentration is used in terms of less than 20% by volume based on the dry component of the coating composition. Pigment volume concentration = pigment volume / total solids volume.

[0106] Colored pigments are finely ground, insoluble natural or synthetic particles used to impart color when added to paint and coating compositions. Pigments are a class of organic or inorganic substances that are insoluble in water and the medium in which they are used, but which, through high dispersion, give color to colored substances. Pigments used in coatings are well known in the art. Non-limiting examples of pigments include anatine, brookite, cadmium yellow, cadmium red, cadmium green, cobalt orange, cobalt blue, aureolin, cobalt yellow, copper pigments, azurite, violet, blue, Egyptian blue, malachite, Paris green, phthalocyanine blue BN, phthalocyanine green G, verdigris, emerald green, iron oxide pigments, blood red, caput mortuum, oxide red, red ochre, Venetian red, Prussian blue, clay pigments, yellow ochre, raw ochre, calcined ochre, raw palm clay, calcined palm clay, marine pigments (e.g., ultramarine and ultramarine green), and zinc pigments (e.g., zinc white and zinc ferrite).

[0107] Opaque pigments reflect light and are used to make coatings opaque or reduce their transparency. They prevent light transmission and provide the desired brightness and whiteness of the final product. The most commonly used are titanium dioxide (TiO2), barium sulfate, zinc oxide, calcium carbonate, talc, nepheline syenite, and combinations thereof. TiO2 is the most common and preferred. Extenders may also be added to the formulation. Suitable examples of extenders include precipitated calcium carbonate, directly mined calcium carbonate, clean-grade magnesium calcium carbonate (dolomite), clean-grade calcined crushed clay (aluminosilicate), and clean-purified magnesium silicate.

[0108] Coagulants can be components of coating compositions. When a coating is applied to a substrate and dries, the purpose of the coagulant in these compositions is to help the discrete polymer particles present in an aqueous dispersion form a continuous film. The role of the coagulant is to soften the polymer particles, causing them to fuse into a tough, continuous film. Commonly used coagulants include ester alcohols, ethers of esters and glycols, esters, alcohols, amides, and polymers.

[0109] According to one embodiment, the coating composition may contain a water-soluble or water-dispersible potential crosslinking agent, as described above. According to some embodiments, the crosslinking agent is added during the formulation of the coating agent, rather than (or in addition to) adding it to the aqueous dispersion of the copolymer binder.

[0110] In one embodiment, the coating composition described herein further comprises one or more additives to improve the surface properties of the dried coating. Non-limiting examples include waxes, fluorinated surfactants, silicone surfactants, rhamnolipid-based surfactants, and phosphate ester surfactants. These performance additives are commercially available, for example under names such as Capstone™ and Aquacer. ®Dowsil™, Stepcote ® Commonly used fluorinated surfactants include, for example, fluoroalkanes, perfluoroalkanes, and their derivatives. In one aspect, short-chain fluorinated compounds are preferred. In a preferred aspect, the fluorinated surfactant is anionic C6 fluorocarbons (e.g., Capstone). ® FS-61), and preferably substantially free of PFOS and PFOA. Wax additives can be derived from both fossil and renewable sources and are typically included in aqueous dispersions and coatings to improve water resistance, surface smoothness, and anti-blocking properties. Non-limiting examples include paraffin-based wax emulsions (e.g., BYK's Aquacer 497 and Aquacer 539, Michelman's Michem). ® Emulsion 36840, BASF's Joncryl ® Wax 35). Examples of silicone surfactants may include Dow's DOWSIL™ 211S Additive. Examples of phosphate ester surfactants include Stepan's Stepcote. ® W-877, W-839, and W-843. Stepcote is the preferred choice. ® W-877. Based on the total weight of the aqueous dispersion, the additives used are typically 50 ppm to 5000 ppm, 100 to 4000 ppm, preferably 200 to 3000 ppm, and most preferably 250 to 2500 ppm.

[0111] The coating composition may also contain one or more surfactants discussed in the polymerization section.

[0112] use

[0113] The coating compositions of the present invention can be applied to the surface of various substrates using conventional techniques such as dipping, brushing, flowing, or spraying. Substrates may include, but are not limited to, wood, artificial wood, paper, cardboard, textiles, synthetic resins, ceramics, ferrous metals, non-ferrous metals, stone, concrete, plaster, etc.

[0114] The coating compositions of this invention can be used for indoor or outdoor applications. Available applications may include, but are not limited to, interior and exterior wall coatings, garage floor coatings, metal coatings, rail vehicle coatings, agricultural machinery coatings, automotive parts coatings, log cabin coatings, deck stains, concrete coatings, wood stains, porch or deck coatings, gloss topcoats, road marking paints, kitchen cabinet coatings, automotive refinish paints, lawn and garden equipment coatings, bus and truck topcoats, gloss decorative enamels, metallic primers, light maintenance coatings, furniture coatings, antifouling coatings, appliance coatings, trash can coatings, heavy equipment coatings, industrial equipment coatings, and window frame and decorative enamels.

[0115] When containing pigments, aqueous dispersions can be formulated into paints (coating compositions) of various colors. When applied to a substrate under ambient conditions, the coating composition can form a film on the substrate with or without the aid of a coalescing agent.

[0116] The non-limiting aspects of this invention are summarized below: Aspect 1. An aqueous polymer dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture, wherein, based on the total dry weight of the copolymer, the monomer mixture comprises monomers a), b), c) and d): a) 20-80% by weight of at least one monomer of structure (I): (I)

[0117] Where R 1 It is hydrogen or methyl; R 2 It is a non-cycloalkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is less than 25°C; b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: (meth)acrylate C1-C8 alkyl esters, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives or combinations thereof, optionally bio-based; c) 0.1-10% by weight of at least one olefinic unsaturated monomer comprising at least one functional group, said functional group comprising at least one of the following: carboxyl, phosphate, phosphonate; sulfonate, and / or its acid, and / or salt, and / or anhydride form; hydroxyl; silane; or combinations thereof; and d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer; in: As determined according to ASTM D6866-22 Method B, the copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content; and The minimum film-forming temperature of the aqueous polymer dispersion is 30°C or lower.

[0118] Aspect 2. The aqueous polymer dispersion as described in aspect 1, wherein monomer a) comprises at least 5%, preferably at least 10%, more preferably at least 20%, even more preferably at least 30%, and most preferably at least 40% of biocarbon content, as determined according to ASTM D6866-22 Method B.

[0119] Aspect 3. An aqueous polymer dispersion as described in aspect 1 or aspect 2, wherein said monomer a) comprises at least one of the following: ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-methylbutyl (meth)acrylate, tert-butyl (meth)acrylate, heptyl (meth)acrylate, 2-octyl (meth)acrylate, or a combination thereof, and wherein said monomer a) comprises at least 40% biochar content as determined by ASTM D6866-22 Method B.

[0120] Aspect 4. An aqueous polymer dispersion as described in any one of Aspects 1-3, wherein the monomer a) is selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methylbutyl (meth)acrylate, 2-octyl (meth)acrylate, or combinations thereof.

[0121] Aspect 5. An aqueous polymer dispersion as described in any one of Aspects 1-4, wherein said monomer b) comprises at least one of the following: methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, styrene, or a combination thereof.

[0122] Aspect 6. An aqueous polymer dispersion as described in any one of Aspects 1-5, wherein said monomer c) comprises at least one of the following: a carboxylic acid functionalized monomer, a phosphorus-containing monomer, a sulfur-containing monomer, a hydroxyl group or a silane or a combination thereof.

[0123] Aspect 7. An aqueous polymer dispersion as described in any one of Aspects 1-6, wherein the monomer c) comprises at least one of the following: (meth)acrylic acid, phosphate ester, sulfate ester, hydroxyalkyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, (meth)acryloyloxyalkyltrialkoxysilane, vinyltrialkoxysilane, or a combination thereof.

[0124] Aspect 8. An aqueous polymer dispersion as described in any one of Aspects 1-7, wherein the monomer c) is selected from the group consisting of acrylic acid, methacrylic acid, or combinations thereof.

[0125] Aspect 9. An aqueous polymer dispersion as described in any one of Aspects 1-8, wherein said monomer d) comprises at least one of: acrylamide, (meth)acrylamide, diacetone acrylamide; (meth)acrylate having at least one of a urea group, urea or thiourea in the side chain; urethane acrylate; aminoalkyl (meth)acrylate; dialkylamino (meth)acrylate; or combinations thereof.

[0126] Aspect 10. An aqueous polymer dispersion as described in any one of Aspects 1-9, wherein the monomer d) is selected from the group consisting of acrylamide, (meth)acrylamide, diacetone acrylamide, ureoyl (meth)acrylate, or combinations thereof.

[0127] Aspect 11. An aqueous polymer dispersion as described in any one of Aspects 1-10, comprising at least 0.1% by weight of at least one additional radical reactive compound, said additional radical reactive compound comprising at least one of: a chain transfer agent; a copolymerizable surfactant; a monomer comprising two or more unsaturated carbon-carbon double bonds; or a combination thereof.

[0128] Aspect 12. An aqueous polymer dispersion as described in any one of Aspects 1-11, wherein the total percentage of monomers a), b), c), d) and optional radical reactive compounds is 100%.

[0129] Aspect 13. An aqueous polymer dispersion as described in any one of Aspects 1-12, wherein the copolymer comprises: 45-60% by weight of monomer a), wherein monomer a) comprises at least one of the following: ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methylbutyl (meth)acrylate, 2-octyl (meth)acrylate or a combination thereof. 40-55% by weight of monomer b), wherein monomer b) comprises at least one of the following: methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate or a combination thereof; 0.1-10% by weight of monomer c), wherein monomer c) contains at least one carboxylate functional group and / or its acid, and / or salt, and / or anhydride form; 0.1-10% by weight of monomer d), wherein monomer d) comprises at least one of the following: (meth)acrylamide, diacetone acrylamide, or a combination thereof; and The copolymer, as determined by ASTM D6866-22 Method B, contains at least 22% biochar content; and The minimum film-forming temperature of the aqueous polymer dispersion is below 30°C.

[0130] Aspect 14. An aqueous polymer dispersion as described in any one of Aspects 1-13, wherein the copolymer comprises a monomer containing at least one carbonyl group capable of reacting with a potential crosslinking agent, said monomer preferably containing at least one 1,3-dicarbonyl group, more preferably containing diacetone acrylamide.

[0131] Aspect 15. The aqueous polymer dispersion of any one of aspects 1-14 further comprises at least one additive.

[0132] Aspect 16. An aqueous polymer dispersion as described in aspect 15, wherein the additive comprises at least two hydrazine and / or acylhydrazine moieties.

[0133] Aspect 17. An aqueous polymer dispersion as described in aspect 14 or aspect 15, wherein the additive comprises an alcohol phosphate surfactant or a salt thereof, preferably potassium n-octyl phosphate, sodium n-octyl phosphate or lithium n-octyl phosphate, more preferably potassium n-octyl phosphate.

[0134] Aspect 18. A coating composition comprising an aqueous polymer dispersion as described in any one of aspects 1-17.

[0135] Aspect 19. A coating composition comprising an aqueous polymer dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture, the monomer mixture comprising monomers a), b), c) and d) based on the total dry weight of the copolymer: a) 20-80% by weight of at least one monomer of structure (I): (I)

[0136] Where R 1 It is hydrogen or methyl; R 2 It is a non-cycloalkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is less than 25°C; b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: (meth)acrylate C1-C8 alkyl esters, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives or combinations thereof. c) 0.1-10% by weight of at least one olefinically unsaturated monomer comprising at least one functional group, said functional group comprising at least one of the following: carboxyl, phosphate, phosphonate, sulfonate; and / or its acid, and / or salt, and / or anhydride form; hydroxyl; silane; or combinations thereof; and d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer in: According to ASTM D6866-22, the copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content; and The minimum film-forming temperature of the aqueous dispersion is below 30°C.

[0137] Aspect 20. The coating composition of aspect 19, wherein the copolymer further comprises at least 0.1% by weight of at least one additional radical reactive compound, said additional radical reactive compound comprising at least one of the following: a chain transfer agent; a copolymerizable surfactant; a monomer comprising two or more unsaturated carbon-carbon double bonds; or a combination thereof.

[0138] Aspect 21. The coating composition as described in aspect 19 or aspect 20, wherein the copolymer comprises a monomer containing at least one carbonyl group capable of reacting with a potential crosslinking agent, said monomer preferably containing at least one 1,3-dicarbonyl group, more preferably diacetone acrylamide.

[0139] Aspect 22. The coating composition as described in any one of Aspects 19-21 further comprises at least one additive.

[0140] Aspect 23. The coating composition as described in aspect 22, wherein the additive comprises at least two hydrazine and / or acylhydrazine portions.

[0141] Aspect 24. The coating composition as described in aspect 22 or aspect 23, wherein the additive comprises an alcohol phosphate surfactant or a salt thereof, preferably potassium n-octyl phosphate, sodium n-octyl phosphate or lithium n-octyl phosphate, more preferably potassium n-octyl phosphate.

[0142] Example

[0143] method: Latex curd The amount of condensate can be measured by filtering the aqueous dispersion polymer through 40-mesh and 250-mesh stainless steel wire mesh filters to capture fine solids formed during emulsion polymer production. The filters are carefully and thoroughly rinsed with water, leaving only the filtered latex solids. The filters are then dried in an oven at 135°C for at least 20 minutes. The amount of filterable solids retained on the 40-mesh and 250-mesh filters is determined by gravimetric analysis, and the total amount is calculated based on the dried dispersion solids.

[0144] Glass transition temperature

[0145] The glass transition temperature can be measured using differential scanning calorimetry (TA Instrument Q2000) at a rate of 10 °C / min. The half-maximum inflection point of the third heating cycle is reported as the midpoint glass transition temperature. According to some embodiments, the glass transition temperatures of the homopolymers are those reported in the 4th edition of *Polymer Handbook*; J. Brandrup (ed.), EH Immergut (ed.), EA Grulke (ed.); ISBN: 978-0-471-47936-9, mid-May 2003. According to some embodiments, the glass transition temperature of the copolymer is calculated using the Fox equation from the homopolymer glass transition temperatures of its monomers (as described in the 4th edition of *Polymer Handbook*).

[0146] Minimum film formation temperature

[0147] The minimum film-forming temperature was measured on a custom-made rectangular aluminum strip with a hard-coated anodized Teflon surface. This strip was equipped with heating and cooling devices, allowing for a linear temperature gradient from 0°C to 60°C over a 34-inch range at 1.77°C / inch. 1–2 ml of wet latex sample was transferred into the orifice of the custom-made stainless steel coating bar, forming a wet film thickness of 0.3 mils. A smooth, linear coating was prepared from one end of the temperature gradient range to the other. A clear cap was then immediately placed on top, and nitrogen was purged to create laminar flow at approximately 15–20 psig, allowing the film to dry for 30 minutes to 1 hour. The minimum film-forming temperature was determined as the point at which the latex formed a clear, crack-free film.

[0148] Scrub resistance

[0149] Relative scrub resistance was evaluated on a Gardner Straight Line Washability and Wear Abrasion Machine according to ASTM D2486-17 Method B. Paints and control paints were applied side-by-side to Leneta Black scrub test plates using a drawdown bar with a 7-mil gap and dried for 7 days at 77 ± 2°F and 50% ± 5% RH in a temperature and humidity controlled (CT / CH) chamber. After curing, the coated plates were placed on two 12.7 x 0.25 mm (0.5 inch x 0.01 inch) pads positioned below each paint on the straight line scrub machine. The paints were then scrubbed with a brush and abrasive scrubbing media until each paint film was removed at a continuous fine line on the respective pad. The test was performed three times, and the number of failure cycles and the ratio between each test paint and the control paint were recorded.

[0150] Anti-adhesion

[0151] Test coatings were prepared using a 3-milk-shaped scraper on a Lenata 3B opacity card. The films were dried for one day in a temperature- and humidity-controlled (CT / CH) chamber at 25°C and 50% relative humidity (RH). In the room temperature (RT) adhesion test, two 2.54 cm x 2.54 cm square strips were placed together, film to film, at a weight of 454 g. After 24 hours, the strips were separated and evaluated. For the high temperature (ET) adhesion test, the paint strips, after drying for 1 day at CT / CH, were placed in a 120°F oven for 30 minutes. A 1000 g weight was transferred onto the film using a 2.54 cm diameter rubber stopper. The film was allowed to cool for 30 minutes before assigning an adhesion rating. Room temperature and high temperature adhesion were rated according to the ASTM D-4946 scale, from 0 (worst) to 10 (best). Tests were performed three times, and the average value was reported.

[0152] Stain resistance

[0153] Stain resistance was measured according to ASTM D4828-94 (2020). Each painted sample was prepared using a coating scraper with a 7-mil gap, with the painted sample and control paints applied side-by-side on a black Lenata scrub card. After drying for three days in a temperature and humidity controlled (CT / CH) chamber at 77 ± 2°F and 50% ± 5% RH, the plates were stained with various dyeing media, covering both paints in a direction perpendicular to the paint application direction. Liquid stains (e.g., coffee and wine) were held in place using single-layer paper towel strips. To ensure good contact with the sample, slight pressure was applied along the entire length of the saturated strip. For this stain resistance test group, the following staining media were applied: mustard [French's], ketchup [Heinz], coffee (French Roast), red wine [Carlo Rossi], grape juice [Concord], ballpoint pen (blue), pencil (2B), purple crayon [Crayola], orange washable marker (Crayola), and red lipstick [Covergirl]. After staining, all samples were allowed to stand for 2 to 2.25 hours after the last stain was applied. After the contact time, excess staining material was rinsed off under cold water and the plates were placed in a [Paul N. Gardner Company, Inc.] scrubber model D10. Two sponges with special brush holders were used, one for each stain. Stain washing included using 10 mL Formula 409. ® The solution was added to a pre-wetted (with water) sponge. The Gardner scrubber was run for 100 cycles. After the test, the plate was rinsed and dried overnight. The change in ΔE value of the stained area was reported compared to the plate portion before staining and washing. A lower ΔE value indicates a lighter stain.

[0154] Coloring strength

[0155] The tinting strength of the white paint was measured according to ASTM D4838-88 (2016). In this test, 5.0 g of phthalocyanine blue colorant [Evonik's Colortrend 888-7214, Colorant E] was added to 250.0 g of base paint and then mixed for 5 minutes on a RedDevil shaker. The tinted paint was applied to a Lenata 1B card using a coating stick with a 10 mil gap, and immediately rubbed 30 times on both sealed and unsealed areas. The CIE-Y reflectance was taken, and the average of the three measurements was reported. The contrast tinting strength was calculated from the Y reflectance data of the sample and the selected control according to the Kubelka-Munk formula:

[0156] Example 1: Preparation of Adhesive

[0157] An initial feed was introduced into a 1-gallon reactor: 515 g deionized water, 2.4 g anionic surfactant I, 7.85 g acrylamide (30%), and 20 g pre-formed seed latex. A monomer pre-emulsion was prepared by mixing 511.04 g ethyl acrylate, 312.32 g methyl methacrylate, 96.18 g isobutyl acrylate, 18 g diacetone acrylamide, and 7.19 g methacrylic acid with 33.65 g anionic surfactant II, 9.20 g anionic surfactant III, 9.7 g anionic surfactant IV, 4.2 g anionic surfactant V, and 252 g deionized water. An initial initiator was prepared by weighing 0.53 g sodium persulfate in a second glass beaker and dissolving it in 8 g deionized water. A delayed initiator was prepared by dissolving 1.1 g ammonium persulfate in 41.5 g water in a third beaker. The reactor contents were heated to 90 ± 2 °C. The initial initiator was introduced into the reactor first. The monomer pre-emulsion and delayed initiator were then fed into the reactor over 210 minutes, while maintaining the reactor temperature at 90 ± 2 °C. After the delayed initiator and monomer were fed, 27 g of water was added to the reactor. The reactor contents were boiled for 15 minutes, and then the medium was cooled to 65 °C. During the 15-minute boiling process, a post-oxidant solution containing 1.9 g of 70% tert-butyl hydroperoxide and 30 g of deionized water was prepared in a glass beaker. A post-reducing agent solution containing 1.9 g of sodium metabisulfite and 31 g of deionized water was also prepared in a glass beaker. The post-oxidant and post-reducing agent solutions were then fed into the reactor over 60 minutes. The reactor was allowed to cool to room temperature. Then, 9.2 g of adipic acid dihydrazide (in 40 g of water) and 22.5 g of Stepcote were added to the reactor.® W-877. Then, the pH of the latex was adjusted to 7.5 using ammonia.

[0158] Examples 2-5

[0159] The latex was prepared in the same manner as in Example 1. The polymer composition is shown in Table 1.

[0160] Comparative Example 1: Preparation of Adhesives

[0161] The latex was prepared in the same manner as in Example 1. The polymer composition is shown in Table 1.

[0162] Comparative Example 2: Preparation of Adhesives

[0163] The latex was prepared in a manner similar to Comparative Example 1. An additional 19 g of Cavasol was added to the reactor at the start of the reaction. ® W7 M TL [Methyl-β-cyclodextrin, solubilizer, Wacker]. Even in the presence of a "phase transfer catalyst" (US5521266), the polymerization of compositions containing lauryl methacrylate was not as pure as the products of the binders in Examples 1-5 (higher filterable solids content). The polymer composition is shown in Table 1.

[0164] Comparative Example 3: Preparation of Adhesives

[0165] The latex was prepared in a manner similar to that of Example 5, but without Stepcote. ® W-877.

[0166] Table 1. Composition of polymeric adhesives (by monomer weight percentage)

[0167] EA = Ethyl acrylate, iBA = Isobutyl acrylate, 2-MBA = 2-Methylbutyl acrylate, 2-OA = 2-Octyl acrylate, LMA = Lauryl methacrylate, MMA = Methyl methacrylate, BA = Butyl acrylate, MAA = Methacrylic acid, AM = Acrylamide, DAAM = Diacetone acrylamide BCC calculations are based on the total bio-based carbon from partially or fully bio-based monomers a) and b) divided by the total carbon content in monomers a), b), c), d) and any additional monomers.

[0168] BCC = 100 x [(moles of bio-based carbon) / (moles of total carbon)]

[0169] Examples 6-10. Preparation of coating compositions

[0170] The above-described aqueous dispersions of Examples 1-5 were evaluated in the coating compositions shown in Table 2 and are named Examples 6-10 in Table 3.

[0171] Comparative Examples 4-6: Preparation of Coating Compositions

[0172] The above-mentioned aqueous dispersions, Comparative Examples 1, 2 and 3, were evaluated in the coating compositions shown in Table 2 and named Comparative Examples 4, 5 and 6 in Table 3.

[0173] Table 2. Coating Compositions

[0174] The coating properties of each adhesive material are shown in Table 3.

[0175] Table 3. Coating performance.

[0176]

[0177] Surprisingly, the color strength and stain removal rate of the copolymer containing lauryl methacrylate were worse than those of coatings prepared using binders containing lower (C1-C8) alkyl ester monomers of acrylic acid. Most notably, the clean removal of lipstick stains was a significant challenge for the copolymer containing lauryl methacrylate, as shown in the photographs and the ΔE values ​​measured at the top of each photograph. A higher ΔE indicates a greater degree of staining due to a darker color left by the dye. The differences in stain resistance and stain removal between the examples of the present invention (Examples 6-10) and the comparative examples (Comparative Examples 4 and 5) are also demonstrated by the total ΔE values ​​in Table 3, which are the sum of the 10 stains tested. Lower ΔE values ​​are more desirable. Comparative Example 6, compared to Example 10, shows the effect of the hydroxyl phosphate surfactant on anti-adhesion. Higher numbers indicate better anti-adhesion properties.

[0178] In this specification, embodiments have been described in a manner that allows for clear and concise explanation; however, it is intended and should be understood that embodiments may be combined or separated in various ways without departing from the invention. For example, it should be understood that all preferred features described herein apply to all aspects of the invention described herein.

[0179] The foregoing description of various forms in this application is for illustrative and explanatory purposes. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications or variations are possible in light of the foregoing teachings. The forms discussed have been chosen and described to provide the best illustration of the principles of the invention and its practical application, thereby enabling those skilled in the art to utilize the invention in various forms and with various modifications suitable for particular uses. All such modifications and variations fall within the scope of the invention as defined by the appended claims and should be interpreted in accordance with the scope to which they are fairly, legally, and equitably enjoyed.

Claims

1. An aqueous polymer dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture, wherein the monomer mixture comprises monomers a), b), c) and d) based on the total dry weight of the copolymer: a) 20-80% by weight of at least one monomer of structure (I): (I) Where R 1 It is hydrogen or methyl; R 2 It is a non-cyclic alkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is less than 25°C; b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: C1-C8 alkyl methacrylates, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives or combinations thereof, optionally bio-based; c) 0.1-10% by weight of at least one olefinic unsaturated monomer comprising at least one functional group, said functional group comprising at least one of the following: carboxyl, phosphate, phosphonate; sulfonate, and / or its acid, and / or salt, and / or anhydride form; hydroxyl; silane; or combinations thereof; and d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer; in: As determined according to ASTM D6866-22 Method B, the copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content; and The minimum film-forming temperature of the aqueous polymer dispersion is 30°C or lower.

2. The aqueous polymer dispersion as described in claim 1, wherein, As determined according to ASTM D6866-22 Method B, monomer a) contains at least 5%, preferably at least 10%, more preferably at least 20%, even more preferably at least 30%, and most preferably at least 40% biocarbon content.

3. The aqueous polymer dispersion of claim 1 or claim 2, wherein the monomer a) comprises at least one of the following: ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-methylbutyl methacrylate, tert-butyl methacrylate, heptyl methacrylate, 2-octyl methacrylate, or a combination thereof, and wherein the monomer a) comprises at least 40% biochar content as determined by ASTM D6866-22 Method B.

4. The aqueous polymer dispersion according to any one of claims 1-3, wherein the monomer a) is selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methylbutyl (meth)acrylate, 2-octyl (meth)acrylate, or combinations thereof.

5. The aqueous polymer dispersion according to any one of claims 1-4, wherein the monomer b) comprises at least one of the following: methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, styrene, or a combination thereof.

6. The aqueous polymer dispersion according to any one of claims 1-5, wherein the monomer c) comprises at least one of the following: a carboxylic acid functionalized monomer, a phosphorus-containing monomer, a sulfur-containing monomer, a hydroxyl group or a silane or a combination thereof.

7. The aqueous polymer dispersion according to any one of claims 1-6, wherein the monomer c) comprises at least one of the following: (meth)acrylic acid, phosphate ester, sulfate ester, hydroxyalkyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, (meth)acryloyloxyalkyltrialkoxysilane, vinyltrialkoxysilane, or a combination thereof.

8. The aqueous polymer dispersion according to any one of claims 1-7, wherein the monomer c) is selected from the group consisting of acrylic acid, methacrylic acid, or combinations thereof.

9. The aqueous polymer dispersion according to any one of claims 1-8, wherein the monomer d) comprises at least one of the following: acrylamide, (meth)acrylamide, diacetone acrylamide; (meth)acrylate with at least one of urea, urea or thiourea in the side chain; urethane acrylate; aminoalkyl (meth)acrylate; dialkylamino (meth)acrylate; or combinations thereof.

10. The aqueous polymer dispersion according to any one of claims 1-9, wherein the monomer d) is selected from the group consisting of acrylamide, (meth)acrylamide, diacetone acrylamide, ureoyl (meth)acrylate, or combinations thereof.

11. The aqueous polymer dispersion of any one of claims 1-10, comprising at least 0.1% by weight of at least one additional radical reactive compound, said additional radical reactive compound comprising at least one of the following: a chain transfer agent; a copolymerizable surfactant; a monomer comprising two or more unsaturated carbon-carbon double bonds; or a combination thereof.

12. The aqueous polymer dispersion according to any one of claims 1-11, wherein the total percentage of said monomers a), b), c), d) and optional free radical reactive compounds is 100%.

13. The aqueous polymer dispersion of any one of claims 1-12, wherein the copolymer comprises: 45-60% by weight of monomer a), wherein said monomer a) comprises at least one of the following: ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-methylbutyl (meth)acrylate, 2-octyl (meth)acrylate or a combination thereof; 40-55% by weight of monomer b), wherein said monomer b) comprises at least one of the following: methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate or a combination thereof; 0.1-10% by weight of monomer c), wherein said monomer c) comprises at least one carboxylate functional group and / or its acid, and / or salt, and / or anhydride form; 0.1-10% by weight of monomer d), wherein said monomer d) comprises at least one of the following: (meth)acrylamide, diacetone acrylamide, or a combination thereof; and in, The copolymer contains at least 22% biochar, as determined by ASTM D6866-22 Method B; and The minimum film-forming temperature of the aqueous polymer dispersion is less than 30°C.

14. The aqueous polymer dispersion of any one of claims 1-13, wherein the copolymer comprises a monomer containing at least one carbonyl group capable of reacting with a potential crosslinking agent, the monomer preferably comprising at least one 1,3-dicarbonyl group, more preferably comprising diacetone acrylamide.

15. The aqueous polymer dispersion according to any one of claims 1-14, further comprising at least one additive.

16. The aqueous polymer dispersion of claim 15, wherein the additive comprises at least two hydrazine and / or acylhydrazine portions.

17. The aqueous polymer dispersion of claim 14 or claim 15, wherein the additive comprises an alcohol phosphate surfactant or a salt thereof, preferably potassium n-octyl phosphate, sodium n-octyl phosphate or lithium n-octyl phosphate, more preferably potassium n-octyl phosphate.

18. A coating composition comprising an aqueous polymer dispersion as described in any one of claims 1-17.

19. A coating composition comprising an aqueous polymer dispersion, said dispersion comprising at least one copolymer formed by emulsion polymerization of a monomer mixture, said monomer mixture comprising monomers a), b), c) and d) based on the total dry weight of said copolymer: a) 20-80% by weight of at least one monomer of structure (I): (I) Where R 1 It is hydrogen or methyl; R 2 It is a non-cyclic alkyl group of C1-C8, preferably C2-C6, more preferably C2-C4, and wherein the glass transition temperature (Tg) of the homopolymer of monomer a) is less than 25°C; b) 20-80% by weight of at least one olefinic unsaturated monomer different from a), selected from the group consisting of: (meth)acrylate C1-C8 alkyl esters, ethylene, vinyl acetate, ethylene tert-carbonate, styrene, styrene derivatives or combinations thereof. c) 0.1-10% by weight of at least one olefinically unsaturated monomer comprising at least one functional group, said functional group comprising at least one of the following: carboxyl, phosphate, phosphonate, sulfonate; and / or its acid, and / or salt, and / or anhydride form; hydroxyl; silane; or combinations thereof; and d) 0.1-10% by weight of at least one nitrogen-containing olefinic unsaturated monomer in: According to ASTM D6866-22, the copolymer contains at least 5%, preferably at least 10%, more preferably at least 15%, and most preferably at least 22% biochar content; and The minimum film-forming temperature of the aqueous dispersion is below 30°C.

20. The coating composition of claim 19, wherein the copolymer further comprises at least 0.1% by weight of at least one additional radical reactive compound, said additional radical reactive compound comprising at least one of the following: a chain transfer agent; a copolymerizable surfactant; a monomer comprising two or more unsaturated carbon-carbon double bonds; or a combination thereof.

21. The coating composition of claim 19 or claim 20, wherein the copolymer comprises a monomer containing at least one carbonyl group capable of reacting with a potential crosslinking agent, said monomer preferably containing at least one 1,3-dicarbonyl group, more preferably diacetone acrylamide.

22. The coating composition according to any one of claims 19-21, further comprising at least one additive.

23. The coating composition of claim 22, wherein the additive comprises at least two hydrazine and / or acylhydrazine portions.

24. The coating composition of claim 22 or claim 23, wherein the additive comprises an alcohol phosphate surfactant or a salt thereof, preferably potassium n-octyl phosphate, sodium n-octyl phosphate or lithium n-octyl phosphate, more preferably potassium n-octyl phosphate.

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